Synthesis of Unnatural C-2 Amino Acid Nucleosides Using NIS-Mediated Ring Opening of 1,2-Cyclopropane Carboxylated Sugar Derivatives

We have developed a general and efficient method for the stereoselective construction of pyrimidine-based pyranosyl C-2 amino acid nucleosides using NIS-mediated ring opening of 1,2-cyclopropanated sugar derivatives. This methodology has been successfully extended to the synthesis of furanosyl nucleosides, Which have potential applications in the development of novel, nontoxic antifungal therapeutics.

New initiators for the ring-opening thermal polymerization of hexachlorocyclotriphosphazene: synthesis of linear poly(dichlorophosphazene) in high yields

Ring-opening thermal polymerization of hexachlorocyclotriphosphazene (N3P3C&h)a s been investigated at 250 "C and at 1.333-Pa pressure using chlorocyclotriphosphazenes N3P3C15(N=PPh3) and N3P3Cl,.,(NMe2), (n = 2-4), salt hydrates, triphenylphosphine, and benzoic acid as initiators. The linear poly (dich1orophosphazene) products are phenoxylated, and the phenoxy polymers are characterized by gel permeation chromatography and dilute solution viscometry. Among the various initiators investigated, CaS04.2H20b rings about a high conversion (>60%) of N3P3C&to the linear [NPC12], polymer which possesses a high molecular weight (>5 X lo6). The rationale for the choice of the initiators and possible mechanism(s) of polymerization is discussed. Several mixed substituent polymers, [NP(OPh),(OC6H4Me-p)2,1, and [NP(OPh),(OCHzCF3)2,]nh, ave been prepared and their thermal properties evaluated.

Automated estimation of fatigue crack length and closure/opening stress

An experimental technique is proposed for the estimation of crack length as well as crack closure/opening stress during fatigue crack growth. A specially designed, single cantilever, crack opening displacement gauge is used to monitor these variables during fatigue crack propagation testing. The technique was experimentally validated through electronfractography.

Role of orbital symmetry in transition metal promoted ring opening reactions of methylenecyclopropanes and cyclobutenes

Transition metals catalyse a variety of organic reactions, of which the ring opening of strained ring organic molecules generated a lot of interest. Theoreticians predicted a metal orbital catalysed pathway, which involved concerted bond breaking and bond forming. On the other hand experimentalists were able to show that the reaction was not proceeding through a concerted pathway by intercepting the intermediates involved. There remained, however, two ring systems methylenecyclopropanes and cyclobutenes—whose reactions with metal complexes seemed to be of a concerted nature. An analysis of the reactions of different metal complexes with these ring systems and the theoretical predictions provide a rationale for understanding these reactions.

AE energy release during the fracture of HSC beams

An attempt has been made experimentally to investigate the acoustic emission (AE) energy release in high-strength concrete (HSC) beams subjected to monotonically increasing load. Acoustic emission energy release during the fracture process of the HSC beams is measured. Stress waves released during the fracture process in materials cause acoustic emissions. AE energy released during the fracture of a notched three-point bend plain concrete beam specimens having 28-day compressive strengths of 50.0 MPa, 69.0 MPa and 78.0 MPa and mortar (cement: sand (1: 4) by weight) specimens are studied. Mortar consists of one part cement and four parts sand by weight. The specimens were tested by a material testing system of 1200 kN capacity employing crack mouth opening displacement control at the rate of 0.0004 mm/s. The fracture energy and the AE energy released during the fracture process of all the tested TPB and mortar specimens are compared and discussed. The observations made in the present experimental study have some applications for monitoring the integrity of structures.

Direct Synthesis of Functionalized Unsymmetrical beta-Sulfonamido Disulfides by Tetrathiomolybdate Mediated Aziridine Ring-Opening Reactions

Direct synthesis of unsymmetrical beta-sulfonamido disulfides by ring-opening of aziridines by using benzyltriethyl-ammonium tetrathiomolybdate 1 as a sulfur transfer reagent in the presence of symmetrical disulfides as thiol equivalents has been reported. Reaction of benzyl and alkyl disulfides gave unsymmetrical beta-sulfonamido disulfides as the only product in very good yields. From the Study, it has been observed that aryl disulfides containing p-NO2, p-Cl, and p-CN led to the formation of the corresponding beta-aminosulfides as the exclusive products. However, un-substituted aryl disulfides and the one containing electron-donating substituents (p-Me) provide a mixture of beta-sulfonamido mono- and disulfides as the products.

Tryst with a molecular and supramolecular oddity: an anti-Furst-Plattner epoxide opening product as a designer additive for accessing an elusive polymorph

Additive induced polymorphism of a conformationally locked tetraacetate 3 in presence of its diastereomer 4 is described. The ester 3 was specially crafted on a trans-decalin backbone to relegate the O-H center dot center dot center dot O H-bond donors to the molecular interior and have the peripheral H-bond acceptors in 1,3-syndiaxial relationship. The supramolecular assembly of 3 was destined to evolve along two mutually exclusive pathways, namely one, which employs intermolecular O-H center dot center dot center dot O H-bonds (pathway 1) and the other that sacrifices these for intramolecular O-H center dot center dot center dot O H-bonds and settles for a crystal packing dictated by weak intermolecular interactions alone (pathway 2). Exploiting the similarity between the self-assemblies of 4 and the two recently reported dimorphs of 3, the ester 3 has been stimulated to follow the elusive non-hierarchical pathway 2 through preferential inhibition of pathway 1. Interestingly, the inhibitor 4 was obtained serendipitously en route 3 via an apparent breakdown of Furst-Plattner rule.

Quantification of impact of a cricket ball

The cricket is one of most popular games in the Asian subcontinent and its popularity is increasing every day. The issue of replacement of the cricket ball amidst the matches is always an uncomfortable situation for teams, umpires and even supporters. At present the basis of the replacement is solely on the judgement, experience and expertise of the umpires, which is subjective, controversial and debatable. In this paper, we have attempted a new approach to quantify the number of impacts or impact factor of a 4-piece leather ball used in the Intemational one-day and test cricket matches. This gives a more objective and scientific basis/ criteria for the replacement of the ball. Here, we have used a well known and widely used Thermal Infra-Red (TIR) imaging to capture the dynamics of the thermal profice of the cricket ball, which has been heated for about 15 seconds. The idea behind this approach is the simple observation that an old ball (ball with a few impacts) has different thermal signature/profice compared to the that of a new ball. This could be due to the change in the surface profice and internal structure, minor de-shaping, opening of seam etc. The TIR video and its frames, which is inherently noisy, are restored using Hebbian learning based FIR (sic), which performs optimal smoothing in relatively less number of iteration. We have focussed on the hottest region of the ball i.e., the inner core and tracked its thermal profice dynamics. Finally we have used multi layer perceptron model (MLP) to quantify the impact factor with fairly good accuracy.

Synthesis of Unnatural Selenocystines and beta-Aminodiselenides via Regioselective Ring-Opening of Sulfamidates Using a Sequential, One-Pot, Multistep Strategy

A variety of N-alkyl-beta-aminodiselenides have been synthesized in high yield from sulfamidates under mild reaction conditions using potassium selenocyanate and benzyltriethylammonium tetrathiomolybdate ([BnNEt3](2)MoS4) in a sequential, one-pot, multistep reaction. The tolerance of multifarious protecting groups under the reaction conditions is discussed. The methodology was successfully extended to the synthesis of selenocystine,3,3'-dialkylselenocystine, and 3,3'-diphenylisoselenocystine and their direct incorporation into peptides.

Ring-Opening-Induced Toughening of a Low-Permittivity Polymer-Metal Interface

Integrating low dielectric permittivity (low-k) polymers to metals is an exacting fundamental challenge because poor bonding between low-polarizability moieties and metals precludes good interfacial adhesion. Conventional adhesion-enhancing methods such as using intermediary layers are unsuitable for engineering polymer/metal interfaces for many applications because of the collateral increase in dielectric permittivity. Here, we demonstrate a completely new approach without surface treatments or intermediary layers to obtain an excellent interfacial fracture toughness of > 13 J/m(2) in a model system comprising copper. and a cross-linked polycarbosilane with k similar to 2.7 obtained by curing a cyclolinear polycarbosilane in air.Our results suggest that interfacial oxygen catalyzed molecularring-opening and anchoring of the opened ring moieties of the polymer to copper is the main toughening mechanism. This novel approach of realizing adherent low-k polymer/metal structures without intermediary layers by activating metal-anchoring polymer moieties at the interface could be adapted for applications such as device wiring and packaging, and laminates and composites.

Observation of crack closure using a crack mouth opening displacement gauge

A crack mouth opening displacement (CMOD) gauge has been designed to estimate the crack length as well as the crack opening stress level in an automated fatigue crack propagation test programme. The CMOD gauge accurately predicts crack tip opening levels in K-controlled tests with constant K, K increasing or K decreasing. In all three K-controlled tests with a single 100% overload cycle, the CMOD gauge does not measure the crack tip opening stress level over a large range of crack lengths after the application of the overload. The CMOD gauge measures the stress level at which the overload plastic zone site opens. Caution should thus be exercised in using the crack opening stress level, estimated by the CMOD gauge, to explain fatigue crack propagation under arbitrary load sequences from the viewpoint of crack closure phenomena.

Synthesis of amino thiols and isocysteines via regioselective ring opening of sulfamidates with tetrathiomolybdate

Herein we present a simple and highly efficient method for the synthesis of beta and gamma-amino thiols via regioselective ring opening of sulfamidates with tetrathiomolybdate 1. The generality of this methodology has been shown by synthesizing carbohydrate derived beta-amino thiol. The scope and versatility of this methodology has been demonstrated by synthesizing biologically important unnatural amino acids like isocysteines in optically pure form. (C) 2011 Elsevier Ltd. All rights reserved.

Re-examination of crack opening model of interface fracture

The complex singularity associated with a crack at the interface between two dissimilar, isotropic and homogeneous materials leads to mathematical artefacts, such as stress oscillations and crack face interpenetrations in the vicinity of the crack tip. To avoid these unrealistic features, Sinclair (Sinclair GB. On the stress singularity at an interface crack. International Journal of Fracture 1980;16(2):111-9) assumed a finite crack opening angle (COA) such that the singularity lambda became real equal to 1/2. This paper extends the COA model by considering real singularities not necessarily equal to 1/2. When COA is 0 degrees: the interface crack singularity is complex with a real part equal to 1/2. On increasing COA, the imaginary part of the singularity decreases and becomes zero at a threshold value of COA; at this point, the singularity is a real, repeated value. A further increase in COA results in a pair of real singularities. Different crack opening configurations and material combinations are studied, and results presented for threshold COAs and associated values of singularity. Stress analyses for these three regimes: (a) complex, (b) real pair and (c) real repeated singularities, are reported. It is seen that additional complexities are present in the last case. Typical results for stress fields are also included for comparing with standard fields. (C) 1999 Elsevier Science Ltd. All rights reserved.